Processs for preparing aromatic olefins using palladacycle catalysis

Abstract

The invention relates to a process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR1## wherein a palladium compound of the formula (IV) ##STR2## is used as a catalyst in the preparation of the compounds of the formula (I).

We claim: 
     
       1. A process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR9## where R 1a  to R 7a  are, independently of one another, hydrogen, C 1  -C 8  -alkyl, alkoxy-(C 1  -C 8 ), acyloxy-(C 1  -C 8 ), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO 2 , OSO 2  CF 3 , CN, COOH, CHO, SO 3  H, NH 2 , NH-alkyl-(C 1  -C 8 ), N-alkyl 2  -(C 1  -C 8 ), NHCO-alkyl-(C 1  -C 4 ), N-alkyl-(C 1  -C 4 )-CO-alkyl-(C 1  -C 4 ), COO-alkyl-(C 1  -C 8 ), CONH 2 , CO-alkyl-(C 1  -C 8 ), NHCOH, NCOO-alkyl-(C 1  -C 4 ), CO-phenyl, COO-phenyl, PO-phenyl 2 , or PO-alkyl 2  -(C 1  -C 4 ), where one of the radicals R 1a  to R 7a  can also be ##STR10## R 8a  is hydrogen, alkyl-(C 1  -C 8 ), phenyl, O-alkyl-(C 1  -C 8 ), or fluorine R 9a  and R 10a  are, independently of one another, hydrogen, CN, CO 2  H, CO 2  -alkyl-(C 1  -C 8 ), CONH 2 , CONH-alkyl-(C 1  -C 4 ), CON(alkyl) 2  -(C 1  -C 4 ), fluorine, CO 2  -phenyl, alkyl, (C 1  -C 8 )phenyl, PO(phenyl), PO(alkyl-(C 1  -C 4 )) 2 , CO-phenyl, CO-alkyl-(C 1  -C 4 ), O-alkyl-(C 1  -C 4 ), NH-alkyl-(C 1  -C 4 ), PO 3  H, SO 3  H, SO 3  -alkyl-(C 1  -C 4 ), SO 2  -alkyl-(C 1  -C 4 ), or O-phenyl, by reaction of haloaromatics of the formula (II) ##STR11##  with olefins of the formula (III) ##STR12##  where R 1a  to R 10a  are as defined above, where one of the radicals R 1a  to R 7a  can also be X and X is iodine, bromine, chlorine, or OSO 2  CF 3 , in the presence of a dipolar aprotic solvent wherein a palladium compound of the formula (IV) ##STR13##  where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are, independently of one another, hydrogen, (C 1  -C 4 )-alkyl, (C 1  -C 4 )-alkoxy, fluorine, NH 2 , NH-alkyl-(C 1  -C 4 ), N-(alkyl) 2  -(C 1  -C 4 ), CO 2  alkyl-(C 1  -C 4 ), OCO-alkyl-(C 1  -C 4 ) or phenyl,   or R 1  and R 2 , R 2  and R 3 , R 3  and R 4 , R 5  and R 6  together form an aliphatic or aromatic ring, and R 7  and R 8  are (C 1  -C 8 )-alkyl, (C 3  -C 12 )-cycloalkyl, or substituted or unsubstituted aryl, and   Q is an anion of an inorganic or organic acid, is used as a catalyst in the reaction between II and III.   
     
     
       2. The process as claimed in claim 1, wherein, in the formula (IV), R 1  to R 6  are, independently of one another, hydrogen, (C 1  -C 4 )-alkyl, or (C 5  -C 8 )-cycloalkyl,   R 7  and R 8  are phenyl, tolyl, xylyl, mesityl, alkyl-(C 1  -C 8 ), or cycloalkyl-(C 5  -C 8 ) and   Q is acetate, propionate, benzoate, chloride, bromide, iodide, fluoride, sulfate, hydrogensulfate, nitrate, tetrafluoroborate, tosylate, mesylate, acetylacetonate, hexafluoroacetylacetonate or pyrazolyl.   
     
     
       3. The process as claimed in claim 1, wherein the catalyst used is one of the compounds trans-di-μ-acetato-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II)   trans-di-μ-chloro-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II)   trans-di-μ-bromo-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II)   trans-di-μ-iodo-bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II)   trans-di-μ-acetato-bis[o-(dimesitylphosphino)-3,5-dimethylbenzyl]dipalladium(II)   trans-di-μ-chloro-bis[o-(dimesitylphosphino)-3,5-dimethylbenzyl]dipalladium(II)   trans-di-μ-bromo-bis[o-(dimesitylphosphino)-3,5-dimethylbenzyl]dipalladium(II)   trans-di-μ-iodo-bis[o-(dimesitylphosphino)-3,5-dimethylbenzyl]dipalladium(II)   trans-di-μ-acetato-bis[o-(t-butyl-o-tolylphosphino)benzyl]dipalladium(II)   trans-di-μ-acetato-bis[o-(di-t-butylphosphino)benzyl]dipalladium(II)   trans-di-μ-acetato-bis[o-(cyclohexyl-o-tolylphosphino)benzyl]dipalladium(II).   
     
     
       4. The process as claimed in claim 1, wherein, the compound of formula (I) is 6-methoxy-2-vinylnaphthalene or 4-(6-methoxynaphthyl)but-3-en-2-one. 
     
     
       5. The process as claimed in claim 1, wherein in formula (I): R 1a  to R 7a  are, independently of one another, hydrogen, (C 1  -C 8 )-alkyl, (C 1  -C 8 )-alkoxy, (C 1  -C 8 )-acyloxy, phenyl, fluorine, chlorine, NO 2 , CN, COOH, CHO, NH-(C 1  -C 8 )-alkyl, N 2 , COO (C 1  -C 8 )-alkyl, CONH 2 , CO-(C 1  -C 8 )-alkyl, CO-phenyl, COO-phenyl, PO-(phenyl) 2 , or OH,   R 8a  is hydrogen, or (C 1  -C 8 )-alkyl   R 8a  and R 10a  are, independently of one another, hydrogen, CN, CO 2  H, CO 2  -(C 1  -C 8 )-alkyl, CO 2  -phenyl, (C 1  -C 8 )-alkyl, CO-phenyl, or CO-(C 1  -C 4 )-alkyl.   
     
     
       6. The process as claimed in claim 1, wherein, in formula (I): R 1a  to R 7a  are, independently of one another, hydrogen, (C 1  -C 8 )-alkyl, (C 1  -C 8 )-alkoxy, phenyl, fluorine, chlorine, NO 2 , CN, COOH, CHO, COO-(C 1  -C 8 )-alkyl, CONH 2 , CO-(C 1  -C 8 )-alkyl, CO-phenyl, PO-(phenyl) 2 , or OH,   R 8a  is hydrogen,   R 9a  and R 10a  are, independently of one another, CN, CO 2  H, CO 2  -(C 1  -C 8 )-alkyl, hydrogen, CO 2  -phenyl, CO-phenyl, or CO-(C 1  -C 4 )-alkyl.   
     
     
       7. The process is claimed in claim 1, wherein, in formula (I), 4 of the radicals R 1a  to R 7a  are hydrogen. 
     
     
       8. The process as claimed in claim 1, wherein, the compound of formula (I) is an alkyloxyvinylnaphthalene, a hydroxyvinylnaphthalene, an acyloxyvinylnaphthalene, a 4-(hydroxynaphthyl)-but-3-en-2-one, a 4-(alkoxynaphthyl)but-3-en-2-one, a 4-(acyloxynaphthyl)but-3-en-2-one. 
     
     
       9. The process as claimed in claim 1, where the dipolar aprotic solvent is a dialkyl sulfoxide, a N,N-dialkylamide, or an alkylated lactam. 
     
     
       10. The process as claimed in claim 9, where the dialkyl sulfoxide is dimethyl sulfoxide, the N,N-dialkylamide is N,N-dimethylacetamide or N,N-dimethylformamide, and the alkylated lactam is N-methyl pyrrolidone. 
     
     
       11. The process as claimed in claim 1, wherein the reaction is carried out at temperatures of from 20 to 200° C. 
     
     
       12. The process as claimed in claim 11, wherein the reaction is carried out at temperatures of from 60° to 180° C. 
     
     
       13. The process as claimed in claim 1 wherein halides of the alkali metals, alkaline earth metals and metals of transition groups 6 to 8 are added.   
     
     
       14. The process as claimed in claim 1, wherein trialkylammonium or tetraalkylammonium, trialkylphosphonium or tetraalkylphosphonium or trialkylarsonium or tetraalkylarsonium salts are added.   
     
     
       15. The process is claimed in claim 1, wherein, in formula (I), 5 of the radicals R 1a  to R 7a  are hydrogen. 
     
     
       16. The process is claimed in claim 1, wherein, in formula (I), 6 of the radicals R 1a  to R 7a  are hydrogen. 
     
     
       17. The process as claimed in claim 12, wherein the reaction is carried out at temperatures of from 100 to 150° C. 
     
     
       18. A process for preparing monofunctional, bifunctional or polyfunctional aromatic olefins of the formula (I) ##STR14## where R 1a  to R 7a  are, independently of one another, hydrogen, C 1  -C 8  -alkyl, alkoxy-(C 1  -C 8 ), acyloxy-(C 1  -C 8 ), O-phenyl, phenyl, fluorine, chlorine, bromine, iodine, OH, NO 2 , OSO 2  CF 3 , CN, COOH, CHO, SO 3  H, NH 2 , NH-alkyl-(C 1  -C 8 ), N-alkyl 2  -(C 1  -C 8 ), NHCO-alkyl-(C 1  -C 4 ), N-alkyl-(C 1  -C 4 )-CO-alkyl-(C 1  -C 4 ), COO-alkyl-(C 1  -C 8 ), CONH 2 , CO-alkyl-(C 1  -C 8 ), NHCOH, NCOO-alkyl-(C 1  -C 4 ), CO-phenyl, COO-phenyl, PO-phenyl 2 , or PO-alkyl 2  -(C 1  -C 4 ), where one of the radicals R 1a  to R 7a  can also be ##STR15## where R 8a  is hydrogen, alkyl-(C 1  -C 8 ), phenyl, O-alkyl-(C 1  -C 8 ), or fluorine, and R 9a  and R 10a  are, independently of one another, hydrogen, CN, CO 2  H, CO 2  -alkyl-(C 1  -C 8 ), CONH 2 , CONH-alkyl-(C 1  -C 4 ), CON(alkyl) 2  -(C 1  -C 4 ), fluorine, CO 2  -phenyl, alkyl, (C 1  -C 8 )phenyl, PO(phenyl), PO(alkyl-(C 1  -C 4 )) 2 , CO-phenyl, CO-alkyl-(C 1  -C 4 ), O-alkyl-(C 1  -C 4 ), NH-alkyl-(C 1  -C 4 ), PO 3  H, SO 3  H, SO 3  -alkyl-(C 1  -C 4 ), SO 2  -alkyl-(C 1  -C 4 ), or O-phenyl, by reaction of haloaromatics of the formula (II) ##STR16##  with olefins of the formula (III) ##STR17##  where R 1a  to R 10a  are as defined above, where one of the radicals R 1a  to R 7a  can also be X and X is iodine, bromine, chlorine, or OSO 2  CF 3 , in the presence of a dipolar aprotic solvent and at least one of a base and 2,6-di-tert-butyl phenol, wherein a palladium compound of the formula (IV) ##STR18##  where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are, independently of one another, hydrogen, (C 1  -C 4 )-alkyl, (C 1  -C 4 )-alkoxy, fluorine, NH 2 , NH-alkyl-(C 1  -C 4 ), N-(alkyl) 2  -(C 1  -C 4 ), CO 2  alkyl-(C 1  -C 4 ), OCO-alkyl-(C 1  -C 4 ) or phenyl,   or R 1  and R 2 , R 2  and R 3 , R 3  and R 4 , R 5  and R 6  together form an aliphatic or aromatic ring,   and R 7  and R 8  are (C 1  -C 8 )-alkyl, (C 3  -C 12 )-cycloalkyl, or substituted or unsubstituted aryl, and   Q is an anion of an inorganic or organic acid, is used as a catalyst in the reaction between II and III.   
     
     
       19. The process as claimed in claim 18, wherein the base and 2,6-di-tert-butyl phenol are present. 
     
     
       20. The process as claimed in claim 18, wherein the base is an amine or an alkali metal salt or alkaline earth metal salt of an acid. 
     
     
       21. The process as claimed in claim 20, wherein the amine is an alkylamine, dialkylamine, or trialkylamine, the alkali metal is lithium, sodium, or potassium, the alkaline earth metal is calcium, or magnesium, and the acid is carbonic acid or an aliphatic or aromatic carboxylic acid.